TW522435B - Slurry, display component and process for producing the display component - Google Patents

Abstract

Provided is a display component, especially a plasma display component, produced by applying the slurry of a urethane compound and an inorganic particle to a substrate, and baking it. The pattern formed has no deficiency.

Description

522435

V. Description of the invention (1) [Technical Field] The present invention relates to a method for manufacturing a glue and a display member using the same. The glue and the manufacturing method of the present invention can be used for the manufacture of various displays starting from plasma displays, plasma-address liquid crystal displays, field emission displays, and image processing of circuit materials. [Prior art]

In recent years, "miniaturization and high-definition of circuit materials and displays" has been sought for an image processing technology that can respond to this. In particular, in the case of forming a partition wall of a plasma display, a method of processing an inorganic material such as glass with high accuracy and a high aspect ratio is desired. Conventionally, a method of performing image processing of an inorganic material is a method of forming an image by photolithography using a photosensitive paste, as proposed in Japanese Patent Application Laid-Open No. 9-310030 and U.S. Patent No. 6,197480. [Disclosure of Invention]

However, when the above-mentioned method removes organic components by firing, the shrinkage force of firing is caused by the paternity of the organic components, and defects such as peeling or disconnection are likely to occur in the image. In other words, the present invention is a paste containing a urethane compound and inorganic fine particles. In addition, the present invention is the glue award of item 1 of the scope of patent application, in which the weight when the temperature rises to 500 ° C and 1000 ° C is expressed by the following formula. (Weight at 500 ° C) / (Weight at 1000 ° C) $ 1.05 In addition, the present invention provides a glue, which is contained in inorganic fine particles and 522435. 5. Description of the invention (2) Organic glue, its characteristics In order to form a thin film by coating the glue on a silicon wafer, and when the temperature is raised to 500 ° C., the maximum value of the average film stress calculated from the difference between the shrinkage of the thin film and the silicon wafer is 0.1 to 20 MPa. In addition, the present invention provides a method for manufacturing a display member, which comprises a step of coating a substrate containing a paste containing a carbamic acid ester compound and inorganic fine particles, and firing the substrate. Moreover, the present invention provides a method for manufacturing a display using the display, particularly a plasma display. A preferred embodiment of the present invention The paste of the present invention contains organic components and inorganic fine particles. In the present invention, the organic component is one in which inorganic fine particles are removed from the cement. The paste of the present invention may be formed by various methods, and then fired, removed organic components, and formed an image substantially formed of an inorganic substance. In the present invention, an image made of a substantially inorganic substance using a paste is suitable for use as a partition wall of a plasma display panel back panel in a display application, that is, a plasma display application. In addition to the urethane compound and inorganic fine particles, the glue used in the present invention may be added with a binder polymer, a dispersant, a plasticizer, a tackifier, an organic solvent, a precipitation preventive agent, and an oxidation preventive agent as required. Wait. The molecular weight of the urethane compound used in the present invention is preferably 15,000 to 50,000. The molecular weight referred to herein is a weight average molecular weight. When it is 15,000 or more, it can maintain the flexibility of the urethane, and can reduce defects such as peeling and disconnection during firing. When it is less than 50,000, the amine can be reduced -4- 522435 V. Description of the invention (3) The viscosity of formic acid vinegar can be easily processed. The urethane compound used in the present invention is, for example, a compound represented by the following general formula (1).

Rl- (R4-R3) n-R4-R2 (1) (wherein 'R1 and R2 represent a substituent selected from an ethylenically unsaturated group, hydrogen, an alkyl group having a carbon number of ˜20, an aryl group, The aralkyl group and the hydroxyaralkyl group may be the same or different; R3 represents an alkylene oxide or alkylene oxide oligomer; R4 represents an organic group containing a urethane bond; n represents 1 (Natural number of ~ 10) The urethane compound preferably contains an ethylene oxide unit. More preferably, R3 in the general formula (1) is an oligomer containing an ethylene oxide unit and a propylene oxide unit, and the content of the ethylene oxide unit in the oligomer is 8 to 70% by weight. When the content of the ethylene oxide unit is 70% by weight or less, flexibility can be improved, and stress during formation of the partition wall can be reduced, so defects such as disconnection of the partition wall can be effectively suppressed. In addition, in the step of firing after improving the thermal decomposition property and forming the partition wall, the problem of firing residue is less likely to occur. In addition, when the content of the ethylene oxide unit is 8% by weight or more, compatibility with other organic components can be improved. The compatibility of organic components can be measured by the haze of a coating film formed by coating the organic components. The haze small line means that the organic components have good compatibility. The haze is preferably 5.0% or less in a coating film having a thickness of 30 // m. Here, the haze (Η: unit%) is based on: Π S K7 1 05 "Test method for optical characteristics of plastics", using an integrating sphere light transmittance measuring device, and measuring total transmittance (Td) of total light transmission Rate (Tt), and by calculating its ratio 値 522435 V. Invention description (4) (H = (Td / Tt) XlOO) Calculate 雾 haze is better than 0.8%, the best is 0.5 %the following. The urethane bond-containing organic group of R4 is preferably formed by the condensation of a diisocyanate group and a hydroxyl group. As the component having a diisocyanate group used herein, an aliphatic diisocyanate compound such as 1,4-diisocyanate butane, 1,6-diisocyanate hexane, and the like, and 1,4-diisocyanate can be used. Aromatic diisocyanate compounds such as acid phenylene ester and tolyl diisocyanate; or alicyclic diisocyanate compounds such as 1,4-cyclohexyl diisocyanate and isophorone diisocyanate. It is preferable to use an alicyclic diisocyanate compound, and it is more preferable to use isophorone diisocyanate, but it is not limited to these. Specific examples of the urethane compound used in the present invention are UA-2 2 3 5PE (molecular weight 18000, EO content rate 20%), UA-3238PE (molecular weight 19000, EO content rate 10%), UA-3 348PE (molecular weight 22000, EO content rate of 15%), UA-2349PE (molecular weight 27000, EO content rate of 7%), UA-5 348PE (molecular weight 39000, EO content rate of 23%) (the above is made by Shin Nakamura Chemical Co., Ltd.), etc., But not limited by these. Moreover, a mixture of these compounds can be used. The content of the urethane compound is preferably 0.1 to 20% by weight in the cement. When the content is 0.1% by weight or more, an appropriate inhibitory effect can be obtained. On the other hand, if it is more than 20% by weight, the dispersibility of the organic component and the inorganic fine particles is reduced, and defects are liable to occur. The glue used in the present invention can be added by reactive monomers, reactive oligomers, reactive polymers, photopolymerization initiators, photoacid generators, photobases 522435. 5. Description of the invention (5) generators , Sensitizer, sensitizing aid, ultraviolet absorber, organic dye, acid, alkali, etc., used as photosensitive glue. Here, the reactivity of the reactive monomers, reactive oligomers, and reactive polymers means that when the dope is irradiated with active light, the reactive monomers, reactive oligomers, or reactive polymers cause photocrosslinking. , Photopolymerization, photolysis polymerization, photomodification, etc., change the chemical structure. In this case, it is possible to manufacture a display member by lithography. It is preferable that the reactive monomer, the reactive oligomer, and the reactive polymer have an ethylenically unsaturated bond. In addition, the concentration of ethylenically unsaturated bonds in the glue is preferably 0.2 to 1.0 mole for the glue before 1 kg of active light irradiation. When the concentration of ethylenically unsaturated bonds in the cement is 0.2 mol or more, the sensitivity of the cement is maintained and the image formation property is good. When the ethylenic unsaturated bond concentration is 1.0 mole or less, the crosslink density at the time of image formation can be maintained in a proper range, and the debonding property is good. In addition, the polymerization and condensation are suppressed by light or heat, and defects such as peeling and disconnection are not easily caused. As the reactive monomer, the dope of the present invention preferably contains an amine compound having an ethylenically unsaturated group. In particular, it is preferable to contain at least one of the amine compounds represented by the following general formula (3) or (4). Because it can increase the sensitivity to light. R5R6R7N (3) R5R6N — M — NR7R8 (4) (where R5 represents a substituent containing an ethylenically unsaturated group; R6, R7, R8 represents a substituent selected from an ethylenically unsaturated group, hydrogen, Carbon number 1 522435 5. Description of the invention (6) ~ 20 alkyl, aryl, aralkyl and hydroxyalkyl groups, r6, r7,

^ ~ SJ are the same or different; M is a divalent bonding group) The substituent R5 of the ethylidene group containing a thiol group of the female compound is any of the following general formulas: (6) and (7) Anything is better. ΟΗ2 = ΟΚ9 — A— (L) a—CH (OH) —CH2— (5) CH2 = CR9— (A) b— (L) a—S〇2— (6) CH2 = CR9— (A) b — (L) a—C〇— ⑺ (wherein R9 is hydrogen or methyl, A is COO, CONH or π or unsubstituted phenylene, and L is selected from carbon number 1 _ @ Of ～ 2〇 or acyclic alkylene, aryl, and square alkyl, L may be an alkyl group, halogen atom, hydroxyl group, aryl group, etc. without _ π or 1 to 6 carbon atoms Instead, and a or b is 0 or 1), more preferably, CH2 = C (CH3) COOCH2CH (OH) CH2-. The amine compound is preferably a tertiary amine compound, and more preferably a compound having a structure represented by the following general formula (8). (CH2 diCR10-C〇-Z) 3-m-NR 'm (8), (wherein R1Q is a hydrogen atom or a methyl group, and R' is an alkyl group, an aryl group, an aralkyl group, or a hydroxyalkyl group , Z is -0-R "-or -NHR"-, R "is alkylene, alkylene, alkylene or hydroxyalkylene, and m is 0, 1 or 2) The best compound used in the invention is bis (2-hydroxy-3 -methacryloxypropyl) isopropylamine. When preparing an amine compound having an ethylenically unsaturated bond, acrylic acid having an ethylenically unsaturated bond can be made. Glycidyl ester, Glycidyl methacrylate, Propylene 522435 V. Description of the invention (7) Acrylic acid chloride, methacrylic acid chloride, acrylic acid anhydride, methacrylic acid anhydride and the like react with amine compounds. An ethylenically unsaturated group-containing compound is mixed. An amine compound having an ethylenically unsaturated bond is, for example, the following compounds, but is not limited to these. In addition, these compounds may be used in combination. In the present invention Depending on its needs, reactive monomers having ethylenically unsaturated bonds other than the above amine compounds can also be used. The reactive monomer If there is more than one photopolymerizable acrylate, methacrylate or propylene-based monomer, etc., the specific examples are alcohols (such as ethanol, propanol, hexanol, octanol, cyclohexanol). , Glycerol, trimethylolpropane, pentaerythritol, etc.), acrylic acid or methacrylate, carboxylic acid (such as acetic acid, propionic acid, benzoic acid, acrylic acid, fluoracrylic acid, succinic acid, maleic acid, phthalic acid, Tartaric acid, citric acid, etc.), reaction product with glycidyl acrylate, glycidyl methacrylate, allyl epoxy, or tetraglycidyl diresorcinol diamine, amidine Derivatives (such as acrylamide, 'methacrylamide, N-hydroxymethacrylamide, methacrylamide, etc.), reactants of epoxy compounds with acrylic acid or methacrylic acid, etc., Unsaturated groups in polyfunctional monomers can also exist as a mixture of propenyl, methacryl, vinyl, and allyl. These can be used alone or in combination. Also, urethanes as reactive oligomers The compound preferably has an ethylenically unsaturated group By reacting the ethylenically unsaturated group of the urethane compound with the ethylenically unsaturated group of the reactive monomer, reactive polymer, etc. contained in the crosslinked material, it is also possible to suppress polymerization shrinkage. 522435 V. Description of the invention ( 8) The glue of the present invention may also contain a copolymer polymer having a carboxyl group. The copolymer having a carboxyl group may be selected from acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, and vinyl acetate. Carboxyl-containing monomers such as esters or these anhydrides, and monomers such as methacrylates, acrylates, styrene, acrylonitrile, vinyl acetate, and 2-hydroxyacrylates, starting with azobisisobutyronitrile It is obtained by copolymerizing the initiator. The copolymer having a carboxyl group is preferably a copolymerized component of acrylic acid or methacrylic acid and acrylic acid or methacrylic acid because of low thermal decomposition temperature during firing. In other words, it is preferable to use a styrene / methyl methacrylate / methacrylic acid copolymer. The acid value of the copolymer having a carboxyl group is preferably 50 to 150 KOH / g. When the acid value is 50 mgKOH / g or less, the allowable development width can be enlarged. In addition, when the acid value is 50 mgKOH / g or more, the resolution of the developer in the exposed portion is not reduced. Therefore, it is not necessary to increase the concentration of the developing solution, and it is possible to prevent the exposed portion from being peeled off, and a fine local image can be obtained. The copolymer having a carboxyl group preferably has an ethylenically unsaturated group in a side chain. Examples of the ethylenically unsaturated group include a propenyl group, a methacryl group, a vinyl group, and an allyl group. A method for adding this side chain to a copolymer, for a thiol group, an amine group, a hydroxyl group, or a carboxyl group in the copolymer, an ethylenically unsaturated compound or acrylic acid chloride having an epoxypropyl group or an isocyanate group , A method for producing by methacrylic acid chloride or chlorinated allyl addition reaction. Examples of ethylenically unsaturated compounds having epoxypropyl groups include acrylic epoxy-10-522435. V. Description of the invention (9) Propyl ester, glycidyl methacrylate, allyl glycidyl ether, ethyl acrylate ring Oxypropyl ester, crotonyl glycidyl ether, glycidyl citrate, glycidyl isocitraconic acid, etc. Examples of the ethylenically unsaturated compound having an isocyanate group include propylene isocyanate, methacrylic acid isocyanate, propyl isocyanate ethyl ester, and methacrylic acid isocyanate. Moreover, the ethylenically unsaturated compound or acrylic chloride, methacrylic acid chloride, or acrylic acid chloride having a glycidyl group or an isocyanate group is 0.05 to thiol group, amine group, hydroxyl group or carboxyl group in the polymer 1 mole equivalent is better. In order to obtain an appropriate exposure amount, it is preferred that the copolymer having a carboxyl group is added in an amount of 10 to 90% by weight of the organic component of the solvent. When the binder component is used as the polymer, polyvinyl alcohol, polyvinyl butanol, methacrylate polymer, acrylate polymer, acrylate-methacrylic acid copolymer, and butyl methacrylate resin can be used. Wait. As the photopolymerization initiator to be used in the present invention, one selected from free radical species can be used. Examples of the photopolymerization initiator include diethoxyacetamiphenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyldimethylacetal, and 1- (4-isopropyl Phenyl) -2 -hydroxy-2-methylpropane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) one, 1-hydroxycyclohexyl- Benzophenone, 1-phenyl-1,2-propanedione- 2- (o-ethoxycarbonyl) oxime, 2-methyl- [4- (methylthio) phenylb- 2-morpholinylpropane -1 -ketone, 2-benzyl-2 -dimethylamino-1-(4-morpholinylphenyl) -butanone-1, phenylene, phenylene ether, phenylene ether, phenylene Isopropyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoin benzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-Benzene

-11- 522435 V. Description of the invention (10) Because of 4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ', 4, 4'-tetra (3rd-but Carbonyl peroxide) benzophenone, 4-benzylfluorenyl-N, N-dimethyl- -carbonyl-2-propanyloxy) ethyl] benzylamine, (4-benzylbenzyl ) Trimethylammonium chloride, 2-hydroxy-3- (4-phenylenephenoxy) -N, N, N-trimethyl-1-propanealuminum chloride monohydrate, 2-isopropylthioxanthone , 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-Cyclo-3-(3,4 -mono ^- 9-Mineral- 9H-Hindi-2-methyloxy) -N, N, N-Dimethyl-1-phenylisopropylamine chloride, 2,4,6-trimethylphenylphenylphosphine oxidation Compounds, 2,2'-bis (o-chlorophenyl) _4,5,4 ', 5'-tetraphenyl-1,2-bisimide D chloroline, 10-butyl-2-acyl chloride D-Danone, 2-ethylanthracene, benzyl, 9, 10-phenanthrenequinone, camphorquinone, methylphenylacetaldehyde, π5-cyclopentenyl-7 / 6-cumenyl-iron ( 1 +) -hexafluorophosphide (1-), diphenyl sulfide derivative, bis (7? 5-2,4-cyclopentadiene-l_yl) _bis (2,6-difluoro- 3- (lH-pyrrole-l-yl)- Based) titanium, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, thioxanthone, 2-methylthioxanthone, 2-thioxanthone chloride 4-benzyl-4-methylbenzophenone, benzophenone, manganese, 2,3-diethoxyethylacetophenone, 2,2-dimethoxy-2 -Phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropylbenzophenone, p-3-3-dichloroacetophenone benzophenone 'benzylmethoxyacetal , Anthraquinone, 2-th-3rd-butylanthraquinone, 2-aminoanthraquinone, lu-chloroanthraquinone, anthrone, benzoanthrone, dibenzocycloheptanone, dimethylmethylanthrone, 4- Azidophenylacetophenone, 2,6-bis (p-azidophenylene) cyclohexane, 2,6-bis (p-azidophenylene) _4_methylcyclohexanone, 2 -Phenyl-1,2-butanedione- 2- (o-methoxycarbonyl) oxime, ι, 3-diphenylpropanetri-12- 522435 5. Description of the invention (11) -Ethoxycarbonyl) oxime, naphthylsulfonyl chloride, quinolinylsulfonyl chloride, N-phenyl acridinone sulfide, 4,4-azobisisobutyronitrile, benzothiazole disulfide , Triphenylphosphine, carbon tetrabromide, tribromophenyl bromide, A combination of photoreductive pigments such as benzene oxide, eosin, methyl blue, and reducing agents such as ascorbic acid and triethanolamine. The present invention can use one or more of these. The photopolymerization initiator is preferably added to the organic component in an amount of 0.05 to 10% by weight, and more preferably 0.1 to 10% by weight. When the addition amount of the photopolymerization initiator is within this range, the residual ratio of the exposed portion and good light sensitivity can be maintained. When the photopolymerization initiator and the sensitizer are used together, the sensitivity can be increased and the effective wavelength range for the reaction can be extended. Specific examples of the sensitizer are 2,4-dimethylxanthones, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,3-bis (4-diethyl Aminoaminobenzo) cyclohexanone, 2, 6-bis (4-dimethylaminobenzo) -4-methylcyclohexanone, Mishlerone, 4,4-bis (diethylamine) Group) benzophenone, 4,4-bis (dimethylamino) phenylpropenebenzene, 4,4-bis (diethylamino) phenylpropenebenzene, p-dimethylaminocinnamon fork Indanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylvinylidene) isonaphthiazole, 1,3-bis (4-dimethylamino) Phenylvinylene) isonaphthiazole, 1,3-bis (4-dimethylaminobenzylidene) acetone, 1,3-carbonylbis (4-diethylaminobenzylidene) acetone , 3,3-carbonylbis (7-diethylaminocoumarin), triethanolamine, methyldiethanolamine, triisopropanolamine, N-phenyl-N-ethylethanolamine, N-phenylethanolamine N-tolyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate-13-V. Description of the invention (12), Isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, (2-dimethylamino) ethyl benzoate, n-butoxy 4-dimethylaminobenzoate ) Ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 3-phenyl-5 -phenylfluorenyltetrazole sulfide, 1-phenyl-5-ethoxycarbon sulfide Azole and so on. One or more of these may be used in the present invention. Moreover, it can also be used as a photopolymerization initiator in a sensitizer. When a sensitizer is added to the glue of the present invention, the added amount is preferably 0.05 to 10% by weight, and more preferably 0.1 to 10% by weight for the organic component. When the addition amount of the sensitizer is within this range, the residual ratio of the exposed portion can be maintained and a good light sensitivity can be obtained. In the present invention, an antioxidant is added. Antioxidants are those with free radical chain inhibition, triple elimination, and decomposition of hydrogen peroxide. The paste contains, for example, a large amount of glass fine particles when it is used in the partition wall of a plasma display member. Therefore, it is difficult to avoid light scattering inside the glue due to the exposure light source, and it is easy to cause the shape of the image next door to become coarse or the depression between the images (and the situation of residual film). The wall of the image next door is cut in vertically, preferably rectangular. Ideally, the exposed dope coating film is soluble in the developing solution at a certain exposure amount or less, and insoluble in the developing solution at the exposure amount or more. In short, the coating film can be dissolved in the developing solution by light scattering even when exposed with a low exposure amount, and even if the exposure amount is increased, the image shape will not be coarsened or a depression will be generated between the images. The larger the range of development, the better. When antioxidants are added to the glue, the antioxidants can return to the base state by capturing the free radicals, the excited photopolymerization initiator or the energy state of the sensitizer, and can suppress excess light reactions by scattering light. Antioxidant-14-522435 V. Description of the Invention (13) The intense photoreaction due to exposure caused by the inhibition can improve the contrast of the dissolution and insolubility of the developer. Specific examples of the antioxidant include p-benzoquinone, naphthoquinone, dimethyl p-benzoquinone, p-toluenequinone, 2,6-dichloroquinone, 2,5-diacetamido-p-benzoquinone, and 2,5-dihexyl. Oxy-p-benzoquinone, hydroquinone, p-3-butylcatechol, 2,5-dibutylhydroquinone, mono-th-butylhydroquinone, 2,5-di-third -Butylpentylhydroquinone, di-3rd-butyl-p-cresol, hydroquinone monomethyl ether, α-naphthol, hydrazine hydrochloride, trimethylbenzyl ammonium chloride, trimethyl Benzyl oxalate, phenyl-cold-naphthylamine, p-benzylphenol, dinaphthyl p-phenylene diamine, dinitrobenzene, trinitrobenzene, picric acid, quinone dioxime, cyclohexyl Ketooxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, benzoin oxime, (2,2'-sulfide bis (4-th-3-octylbenzoate) ) -2-Ethylhexylamine nickel- (II), 4.4'-bis (3-methyl-6-third-butylphenol) sulfide, 2,2'-methylenebis (4-methyl- 6-third-butylphenol), 2,2 bis (4-methyl-6-third-butylphenol), triethylene glycol bis [3- (3-butyl-5-methyl 4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [(3,5- - 3 - butyl-4-hydroxyphenyl) propionate]), 1, 2, 3 - trihydroxybenzene, such as but not limited. The present invention can use one or more of these. The added amount of the antioxidant is preferably from 0.1 to 30% by weight, and more preferably from 0.5 to 20% by weight. By keeping the amount of the antioxidant in this range, the sensitivity of the glue can be maintained, and the degree of polymerization can be maintained to maintain the shape of the image. In addition, when an ultraviolet absorbent is added to the glue, it can be absorbed and exposed. 522435 V. Description of the invention (14) The light source absorbs the scattered light inside the glue and weakens the scattered light. The ultraviolet absorber includes, for example, a benzophenone-based compound, a cyanoacrylate-based compound, a salicylic acid-based compound, a benzotriazole-based compound, an indole-based compound, an inorganic fine-particle metal oxide, and the like. Among these, a benzophenone-based compound, a cyanoacrylate-based compound, a benzotriazole-based compound, or an indole-based compound is particularly effective. Specific examples of these are 2,4-dihydroxybenzophenone, 2-hydroxy-4 -methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy- 4 -methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octyloxydiphenyl Methanone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy 2-hydroxybenzophenone Ketone, 2-hydroxy-4- (2-hydroxy-3-methylpropionyloxy) propoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole , 2- (2'-hydroxy-3, 3rd-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2, -hydroxy-3 ', 5, di- 3-butylphenyl) -5-chlorobenzotriazole, 2- (2, -hydroxy-4, -n-octyloxyphenyl) benzotriazole, 2-ethylhexyl-2- Cyano-3,3-diphenylacrylate, 2-ethyl-2-cyano-3,3-diphenylacrylate, "BONASORB" UA-390 1 ( Orionton (manufactured by Orion Chemical Company), "B0NAS0RB" UA-3902 (manufactured by Orionton Chemical Company), SOM-2-0008 (manufactured by Orionton Chemical Company), etc. These restrictions. In addition, a reactive type in which a methacrylic group or the like is introduced into the framework of these ultraviolet absorbers can also be used. The present invention can use these -16- 522435 V. More than one of the invention description (15). The added amount of the ultraviolet absorber in the cement is preferably 0.001 to 10 wt%, and more preferably 0.005 to 5 wt%. By being in this range, the transparent critical wavelength and wave width can be made within the desired range, the transmittance of the exposure light source and the sensitivity of the glue can be maintained, and the absorption effect of scattered light can be obtained. When the invention aims at exposure and development, an organic dye can be added to the glue. When colored by adding a dye, the applicability is good, and the portion remaining with the glue during development can be easily distinguished from the removed portion. The organic dye is not particularly limited, and it is preferred that it does not remain in the insulating film after firing. Specific examples include anthraquinone dyes, indigo dyes, phthalocyanine dyes, carbon iron dyes, quinone imine dyes, methine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzene Quinone dyes, naphthoquinone dyes, phthaloimine dyes, and the like. In particular, it is better to select the one that absorbs light with wavelengths near the h-line and i-line (such as carbon blue dyes such as basic blue) to obtain the effect of the present invention more easily. The addition amount of the organic dye is preferably 0.001 to 1% by weight. When the viscosity of the glue applied to the substrate is adjusted according to the coating method, an organic solvent may be used. The organic solvent used at this time can be methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutanol, isopropyl Alcohol, tetrahydrofuran, dimethyl sulfene, r-butyrolactone, brominated benzene, chlorinated benzene, dibromobenzene, dichlorobenzene, brominated benzoic acid, chlorobenzoic acid, etc., or more These organic solvent mixtures. -17- 522435 5. Description of the invention (16) The paste of the present invention preferably has an inorganic fine particle content of 40 to 80% by weight. If there are too many organic components, a large amount of substances must be removed in the firing step, so the firing time becomes long and it is difficult to completely inorganicize. In addition, when forming a partition wall having a size for the purpose of increasing the firing shrinkage, it is necessary to thicken the coating film and the like, which is not good in terms of image formability. It is not good to keep the shape of the next door. If the organic component is too small, not only the mixing and dispersion of inorganic particles in the mortar are not sufficient, but also problems such as an increase in the viscosity of the mortar and a decrease in the coatability of the rubber award, and the stability of the mortar is easily affected by adverse effects. Not for desire. In addition, when the dispersibility of the organic component and the inorganic fine particles is low, defects are liable to occur during firing. The inorganic fine particles are preferably made of a filler having 60 to 97% by weight of a low melting point glass powder and 3 to 40% by weight of an average particle diameter of 1 to 4 // m. When the filler is used to control the firing shrinkage rate or maintain the strength of the formed partition wall, it is used together with low melting glass. If it is less than 3% by weight, the addition effect cannot be exhibited, and if it is more than 40% by weight, the problem of reduction in the strength of the partition wall occurs, which is not desirable. The inorganic fine particles may further contain 30% by weight or less of oxide fine particles having an average particle diameter of 0.003 to 0.02 // m. In addition, the refractive index of the low-melting glass powder and the filler is preferably 1.45 to 1.65. The dope is one in which inorganic fine particles are dispersed in an organic solvent system in which organic components are dissolved, and inorganic fine particles having a relatively high concentration are present in the organic component layer of the coating film. When forming an image by lithography in this coating film, the refractive index of each component in a similar paste is better. Since the organic used is -18-522435 5. Explanation of the invention (17) The average refractive index of the components is usually 1.4 ~ 1.7, and the refractive index of the inorganic fine particles is preferably selected in the vicinity of this range. The peeling components made of various oxides have controllable characteristics in view of compatibility, and in the present invention, controlled low-melting glass powders such as thermal characteristics and refractive index can be used. The refractive index of the low melting glass powder is 1.45 ~ 1.65, the glass transition point is 400 ~ 550 ° C, and the load softening point is preferably 450 ~ 600 ° C. By making the load softening point to be 450 ° C or more, the partition wall will not be deformed in the steps after the formation of the component and the display. By making the load softening point to be 600 ° C or less, a melted and high-strength next door. The low-melting glass powder used in the glue is to have good filling and dispersibility during the formation of the glue. When the glue can be coated with a uniform thickness to maintain good image formation, the average particle size is 1 to 4 / / m, the maximum particle size is preferably 3 5 // m or less. The glass powder having this particle size distribution is excellent in filling and dispersing properties of the cement. When the glass powder is a low melting point glass powder, it is almost completely melted and integrated during the firing step, so that a powder having a relatively large particle size can be tolerated. When it is within this range, it is possible to satisfy the filling and dispersing properties, and to form a paste having excellent coatability and image formability. The filling material of the present invention preferably uses at least one selected from the group consisting of high-melting glass with adjusted refractive index and coating with oleic acid. High melting point glass powder is preferably one having a glass transition point of 500 to 1200 ° C and a load softening point of 550 to 1200 ° C. The paste of the present invention can be used as a conductive paste by using metal fine particles as inorganic fine particles. By using this conductive paste, high precision can be obtained -19- 522435 V. Description of the invention (18) A circuit image with fine and few defects. The conductive paste can be used, for example, to form electrodes for a plasma display. The metal fine particles are preferably noble metal conductive fine particles such as Au, Ni, Ag, Pd, and Pt. Various powders can be used alone or in combination. The addition of C r or Rh to these is preferable in terms of improving high-temperature characteristics. When using a photosensitive paste, the average particle size of these metal particles is preferably 0.5 to 5 // ιώ. If the average particle size is less than 0.5 / z m, light cannot pass through the coated film smoothly when exposed to ultraviolet light, and it is difficult to form a fine image with a line width of 60 μm or less for a good conductor. In addition, if the average particle diameter is larger than 5 // m, the surface roughness of the circuit image after coating becomes coarse, the image longitude is reduced, and the nozzle will cause problems. The metal fine particles are preferably those having a specific surface area of 0.1 to 3 m2 / g. If the specific surface area is less than 0.1 m2 / g, the accuracy of the circuit image will decrease. If it is more than 3 m2 / g, the surface area of the powder is too large, the ultraviolet light is scattered, and the image accuracy is lowered. The shape of the metal particles can be flake (plate, cone, rod) or spherical. In order to suppress aggregation, and when there is less ultraviolet scattering during exposure, it is better to use a spherical shape. The paste of the present invention is raised to 500 ° C and 1 000 ° C under a temperature rising condition of 10 ° C / min. The weight measured by the measuring device is preferably expressed by the following formula: 0 (500 ° C weight) / (1000 ° C weight 1.05 500 ° C and 1000 ° C weight ratio are small, which means that the organic component has good debonding. If the above When the ratio is K05 or less, the remaining organic components in the partition wall are -20-522435. 5. The invention description (19) is reduced and the reliability of the display can be improved. By adding a urethane compound to the glue, the weight ratio can be made. Reduced. Especially when the content of ethylene oxide units in the urethane compound is within the above range, it is desirable to make the weight relatively small. Moreover, when the dope contains a compound containing an ethylenically unsaturated group, The above-mentioned weight ratio can be controlled by controlling the concentration of ethylenically unsaturated bonds. The paste of the present invention is coated on a silicon wafer to form a thin film of 3 to 1 0 // m, and from 30 ° C in 1 hour. When the temperature rises to 500 ° C, the following formula can be used to make silicon The maximum value of the average film stress calculated from the wafer difference is 0 · 1 to 20 MPa, more preferably 0.1 to 1 O MPa. The average film stress σ (Pa) = Eh2 / (lu) 6Rt (E / ( 1- u) is the biaxial elasticity coefficient of the substrate, l.SOSxiCTHpa when the above silicon wafer is used !!! is the thickness (m) of the substrate, R is the curvature radius (111) of the substrate, and t is the film Thickness (111)) When the maximum 使 of the average film stress is 0.1 to 20 MPa, shrinkage during firing can be suppressed, firing defects such as peeling or disconnection can be reduced, and firing can be reduced by 0.1 to 10 MPa. Defect. The average film stress can be suppressed by adding a urethane compound to the glue. In addition, when the glue contains a compound containing an ethylenically unsaturated group, the average film stress can be controlled by controlling the concentration of the ethylenic unsaturated agent. Glue usually makes adhesive polymers, dispersants, plasticizers, tackifiers, organic solvents, anti-precipitants, antioxidants, reactive monomers, reactive oligomers, reactive polymers, photopolymerization initiation Agent, photoacid generator, photobase-21-522435 V. Description of the invention (20) Generator Sensitizer, sensitizing aid, ultraviolet absorber, organic dye, acid, alkali and organic solvent are adjusted to a predetermined composition and then homogeneously mixed and dispersed with 3 rollers or kneading machine. The viscosity of the glue can be made of inorganic The addition ratio of microparticles, sensitizers, organic solvents, plasticizers and anti-settling agents is appropriately adjusted, and its range is preferably 2,000 to 200,000 cps (cm · poise). For example, to screen the substrate coating In the printing method, a viscosity of 2000 to 5000 cps is preferred. The screen printing method of the substrate coating method is used to obtain a coating thickness of 1 to 20 // m. When the viscosity is 50,000 to 200,000 cps, good. When a doctor blade coating method or a plastic film coating method is used, a viscosity of 10,000 to 50,000 c p s is preferred. By applying the thus-obtained paste of the present invention to a substrate, forming an image using various methods, and firing, a display member can be obtained. The paste of the present invention is particularly suitable for manufacturing a plasma display device having a partition wall on a substrate. As a method of forming an image, for example, a screen printing method, a sandblasting method, and lithography can be used. Lithoscopy is preferred because it can be processed with high precision. An example of manufacturing a display component using the above-mentioned glue is described by lithography, but the present invention is not limited to these. The substrate is fully or partially coated with glue to form a coating film. The coating method may be a screen printing method, a rod coating method, a roll coating method, a plastic film coating method, a doctor blade coating method, or the like. The coating thickness can be adjusted by selecting the number of coating times, the mesh size of the screen and the viscosity of the glue. Here, the glue is applied to the substrate, and the surface of the substrate is treated in order to improve the adhesion between the substrate and the coating film. The surface treatment liquid can use silane coupling agent-22- 522435 5. Description of the invention (21), such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, ginseng (2-methoxyethyl) Oxy) vinylsilane, r-glycidoxypropyltrimethoxysilane, methylpropoxypropyl) trimethoxysilane, r-(2-aminoethyl) aminopropyltrimethyl Oxysilane, r-chloropropyltrimethoxysilane, r-thiolpropyltrimethoxysilane, r-aminopropyltriethoxysilane, etc., or an organic metal such as organic titanium, organic Aluminum, organic zirconium, etc. The silane coupling agent or organic metal is diluted to a concentration of 0.1 to 5% using an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methanol, ethanol, propanol, butanol, and the like. Then, the surface treatment is uniformly applied to the substrate with a spinner or the like, and then the surface treatment is performed by drying at 80 to 140 ° C for 10 to 60 minutes. After coating, exposure was performed using an exposure device. The exposure device can be a Brochsimiti exposure machine. In addition, in the case of large-area exposure, a large-area exposure can be performed by an exposure machine with a small exposure area by conveying and exposing after coating a paste on a substrate. After exposure, the difference in solubility of the developing solution is developed using the exposed portion and the unexposed portion of the coating film. The development is performed by a dipping method, a spray method, or a brush method. As the developing solution, an organic solvent which can dissolve the organic components in the glue can be used. Further, water can be added within a range that does not lose the organic solvent. The developing liquid is preferably composed of water as the main component. When a compound having an acidic machine such as a carboxyl group is present in the cement, it can be developed with an alkali developing solution. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, or potassium hydroxide aqueous solution can be used. However, it is preferable that the organic alkaline aqueous solution be used to remove the alkaline component during the firing. -23- 522435 5. Description of the invention (22) Organic amine compounds can be used as the organic base. Specific examples include tetramethylammonium hydroxide, trimethylbenzyl ammonium hydroxide, monoethanolamine, and diethanolamine. The concentration of the alkaline aqueous solution is usually 0.05 to 5% by weight, and more preferably ο to 1% by weight. When the alkali concentration is too low, the soluble part cannot be removed, and when the alkali concentration is too high, the image part will be peeled off, and the non-soluble part will be corroded, so it is not desirable. In addition, the development temperature at the time of development is preferably performed at 20 to 50 ° C in terms of step management. Then, it is fired in a firing furnace. The firing atmosphere or temperature varies depending on the type of the paste or the substrate ', and the firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. As the firing furnace, a bath firing furnace or a belt firing furnace can be used. Firing is usually performed at 400 to 1 000 ° C. When performing image processing on a glass substrate, it is preferable to perform firing by maintaining the temperature at 480 to 6 at 10 ° C for 10 to 60 minutes. By the above step ', a display member is formed on the substrate to form an image substantially formed of an inorganic substance. The present invention will be specifically described in the following examples. However, the present invention is not limited by these. The concentration (%) is particularly limited to% by weight. (Examples 1 to 10, Comparative Examples 1 to 2) The urethanes shown in Table 1, 3% by weight polymer solution and dispersant, 3% by weight leveling agent, and 4% by weight were dissolved by heating at 50 ° C. Dipropylene glycol monomethyl ether to prepare an organic solution. It was coated on a glass substrate and dried at 100 ° C for 90 minutes to obtain a thickness of 3 0 // π coated film paste. The haze computer was directly read using a Ska test machine. HGM-2DP was measured. -24- 522435 V. Description of the invention (23) The measurement 値 is shown in Table 2. The inorganic fine particles of Table 1 were added to the above-mentioned organic solution, and kneaded with a kneader to prepare a slurry. The above mortar was measured using a thermogravimetric measuring device "TGA-5 0" manufactured by Shimadzu Corporation and measured in air at a temperature rising rate of IO ° C / min to 500 ° C and 1 000 ° C. weight. The weight of (weight at 500 ° C) / (weight at 1000 ° C) is shown in Table 2. Then, the above-mentioned glue is coated on a Shiyoshi wafer made of Shin-Etsu Semiconductor Co., Ltd. with a diameter of 100 to 0.5 mm and a G degree of 525 to 25 // Π1 to form a coating having a thickness of 3 to 10 / im. Laminated. The film expansion and contraction measuring device "F2300S" manufactured by FLEXUS was used to measure the shrinkage when the temperature was raised from 300 ° C to 500 ° C in one hour. The measured maximum expansion is shown in Table 2. In addition, the above-mentioned paste was coated on a glass substrate to form a coating film having a thickness of 50 // m, and fired at 560 ° C for 15 minutes. After firing, the self-scoring spectrophotometer "U-32 10" manufactured by Yueli Manufacturing Co., Ltd. was used to measure the reflectance of a film formed only of an inorganic substance. Measurements are shown in Table 2. A strip-shaped silver address electrode (line width 100 // m, thickness 3 // m, pitch 5 00 // m) is formed on a 42-inch diagonal glass substrate, and a thickness of 1 5 // m is formed thereon After the electrophoretic layer is used, the above-mentioned paste is used for screen printing of the lower layer. A screen printing plate for the purpose of forming a grid-like partition image for a plasma display (transverse partition: line width 500 // m, image pitch 1 000 // m, longitudinal partition wall: line width 60 // m, drawing (Image distance 500 // m), configured and fixed under the transverse partition wall and the address electrode orthogonally, until the dry thickness of the lower layer is 90 // m -25- 522435 V. Address combination and repeat in the description of the invention (24) Printing 5 ~ 6 times printing and drying. In addition, the above-mentioned glue was used to perform screen printing of the upper band image on the lower grid cell image. Screen printing plate (median wall: line width 60 // m, image spacing 500 // m), fixed in parallel with the address electrode, until the dry thickness of the upper layer is 90 // m, address combination and repeat 5 to 6 times printing and drying. By making the grid-like partition wall image fired at 56 ° C for 15 minutes, a strip-shaped partition wall with a pitch of 500 // m, a line width of 60 // m, and a locality of 130 / zm can be obtained, and The orthogonally spaced 1 000 // m, line width 500 // m, and height 6 0 // m are auxiliary display walls with grid-like partition walls. After firing, observe the defects such as peeling or disconnection. The results are shown in Table 2. Secondly, a fluorescent substance was applied between the partition walls adjacent to the above display member. The fluorescent substance was applied by forming a hole with a diameter of 30 // m and spitting out the fluorescent substance glue from the front end of the nozzle. The display method of the slurry is performed. The phosphor is coated on the side of the partition wall and fired to 25 // m, and the thickness of the fired layer is 25 // m, and fired at 500 ° C for 10 minutes. A back substrate for a plasma display (hereinafter referred to as a PDP) was prepared. A separately prepared front substrate was adhered to the back substrate using a contact glass, and an internal gas pressure of 66,500 Pa was sealed with a neon gas containing 50% xenon. In addition, Install the drive circuit to make the PDP. ○ Reliability of the PDP produced, and place it without lighting 2 After a month, an accelerated test was performed at 70 ° C for 48 hours to measure the operating voltage of -26-522435. V. Description of the invention (25) The voltage increased. The results are shown in Table 2. The voltage increased to 1 V after this accelerated test. It is stable at the following time, slightly increased at 2 to 3 V, and increased at 4 V or higher. -27- 522435 V. Description of the invention (26) Table 1 Types of urethane polymer solution low melting point glass-filled oxide fine particles Adding amount Weight average EO content Kind of adding amount Adding amount Adding amount (%) Molecular weight (%) (%) (%) (%) Example 1 I 10 18000 30% I 20 60 One example 2 Π 10 19000 10% Π 20 40 20 one example 3 m 10 42000 0% I 20 60 one example 4 IV 10 27000 7% Π 20 40 17 3 example 5 V 10 24000 80% I 20 60 one example 6 VI 10 1200 50% Π 20 60-one example 7 I 0.05 18000 30% I 20 60-one example 8 Π 25 19000 10% Π 20 50 5 5 example 9 melon 10 18000 30% I 50 30 one example 10 _ _ _ — I 45 40 5 a comparative example 1 — _ _ _ I 30 60 one a comparative example 2 — one — one 30 30 10 ——— -28- 522435 V. Description of the invention (27) Table 2 Haze of organic coating film (%) Weight ratio (500 ° C / 1000 ° 〇 Maximum stress (MPa) Reflectance (%) Defect (number) Operating voltage example 1 0.2 1.01 6 20 0 Stable example 2 0.3 1.00 5 43 0 Stable example 3 70.0 1.00 4 20 4 Stable example 4 15.0 1.01 3 61 0 Stable example 5 0.1 1.03 13 20 4 Add a little example 6 0.0 1.01 15 20 5 Stable example 7 0.1 1.03 17 20 5 Add a little example 8 0.1 1.00 4 79 3 Settle example 9 0.2 1.04 11 20 4 Add a little example 10 0.0 1.04 16 38 5 Add A little Comparative Example 1 0.0 1.08 24 20 > 50 Increase Comparative Example 2 0.0 1.10 25 48 > 50 Increase (Example 1 1 ~ 2 1, Comparative Examples 3 ~ 4) Heat dissolve at 50 ° C as shown in Table 3 The urethane, amine compound, monomer, and polymer solution and 5% by weight of a photopolymerization initiator, 0.01% by weight of an organic dye, and 5% by weight of r-butyrolactone to prepare an organic solution. Add the inorganic fine particles shown in Table 3 to this organic solution, and use a kneading machine to make a slurry -29- 522435 V. Description of the invention (28) A slurry of organic coating film, 50 (TC and 1 000 ° C) The measurement of the mortar weight at the time, the location of the mortar coating film, and the reflectance of the mortar coating film after firing were performed in the same manner as in Example 1. The measurement is shown in Table 4. The size of the diagonal 42 inches A strip-shaped address silver electrode (line width 5 0 // m, thickness 3 // m, pitch 2 5 0 // m) is formed on the glass substrate, and an electromotive layer having a thickness of 15 // m is formed thereon. The above-mentioned paste has a dry thickness of 90 □ 〇! And is applied and dried. Next, a mask (strip-like image, line width 6 0 0 //) is formed for the purpose of forming a grid-like partition image for a plasma display. m, image spacing 1 0 0 0 // m), configured, fixed, and exposed under the orthogonal contact with the address electrode. At this time, to prevent the photomask from being contaminated, set it between the photomask and the coating surface 100 // m cover. The minimum exposure amount is the smallest exposure amount in the next image without peeling during development. After exposure, apply the above Glue and dry to form a coating film with a dry thickness of 90 // m. On this coating film, a photomask (striped image, line width 30 // m, image spacing 250 // m) and The address electrodes are arranged and fixed in parallel and exposed. After exposure, they are developed in a 0.5% ethanolamine aqueous solution, and then fired at 5 60 ° C for 15 minutes. A pitch of 250 μm and a line width of 30 // m, height 1 30 # m The auxiliary display wall with a grid-like partition wall. After firing, observe the defects such as peeling or disconnection, and the results are shown in Table 4. Second, the adjacent display members A fluorescent substance is applied between the walls. The fluorescent substance is applied by forming a hole with a diameter of 130 // m from the front end of the nozzle -30- 522435 V. Description of the invention (29) Display of the fluorescent substance glue The method is as follows. The phosphor is coated on the side of the partition wall and fired to a thickness of 2 5 m, and the thickness of the fired layer is 25 V m. The firing is performed at 500 ° C for 10 minutes to prepare a plasma. A rear substrate for a display (hereinafter referred to as a PDP). A separately-made front plug plate was adhered to the rear substrate with a contact glass to contain The neon gas of 50% xenon seals the internal air pressure to 66500Pa. In addition, the drive circuit is installed to make the PDP. 〇Reliability of the PDP produced, after being left for 2 months without lighting, at 70 ° C The acceleration test was performed for 48 hours to measure the voltage rise of the operating voltage. The results are shown in Table 4. After the acceleration test, the voltage was stable when the voltage increased below 1 V, increased slightly when 2 to 3 V, and increased when the voltage exceeded 4 V. -31-522435 V. Description of the invention (30) Comparative example 4 Comparative example 3 Example 21 Example 20 Example 19 Example 18 Example 17 Example 16 Example 15 Example 14 Example 13 Example 12 Example 11 1 1 1 1 < a _ jgjj φφ valine formate οο ο ο -Ρ ^ -P ^ CO O o L / i -1 ^ Addition amount (%) 1 1 1 1 1- * t > 〇g 24000 27000 42000 i -18000 19000 18000 19000 18000 Weight-average molecular weight 1 1 1 1 s 〇〇s S OJ S § ο »~ · k S 〇〇DJ > if ο J ~!« I ~ (W w HH w I—ί 1 ㈡ 1 > — * Kinds of amine compounds 0 \ —1 OJ OJ UJ o L > h 〇〇 \ LO Addition (%) 1 ~ I 1 1 ~ ί Η w 11 1 ~ 1 1 ㈡ 1-i 1 1-i 1S ίΤΠΙϋ imim〇1ffln Πίφΐ m ο -j oo OJ oi 4.95 On ο UJ Addition (%) < θ < a < B type polymer solution OJ OJ OJ i; on U〇OJ added amount (%) g L > rt LA g ^ r \ added amount (%) 'low melting point glass-ο 〇◦ 〇ο ο added amount (%) Filler ο ο ο 〇o 〇oo 〇〇ο ο ο Addition amount (%) Oxide fine particles ο ο α \ ο 〇Ν \ 〇O 〇〇v〇〇On o ON On o -0 o 〇〇 〇OJ ο OJ σ \ ο 〇〇OJ ο Concentration of ethylenic discordance (mol / kg) -32- 522435 V. Description of the invention (31) Table 4 Haze (%) weight ratio of organic component coating film (500 ° C / 1000 ° C) Maximum stress (MPa) Reflectance (%) Minimum exposure (mJ / cm2) Defect (number) Operating voltage Example 11 0.2 1.02 6 20 500 0 Stable Example 12 0.3 1.02 5 43 300 0 stable example 13 0.2 1.02 4 20 1100 0 stable example 14 0.3 1.03 13 61 300 0 slightly added example 15 0.1 1.01 5 20 500 4 stable example 16 72.0 1.00 3 20 500 4 stable example 17 15.0 1.02 6 38 400 5 Stability Example 18 0.0 1.04 14 40 400 5 Add a little Example 19 0.0 1.014 13 79 500 4 Stability Example 20 0.0 1.05 17 20 300 7 Add a little Example 21 0.0 1.04 16 45 400 8 Add a little Comparative Example 3 0.0 1.08 24 20 150 > 50 Add a Comparative Example 4 0.0 1.10 25 53 1500 > 50 Add (Example 22 ~ 24. Comparative example 5) The carbamate, amine compound, monomer, and polymer solution shown in Table 5 and 2% by weight of a photopolymerization initiator, and 0.001% by weight of an organic dye were dissolved by heating at 50 ° C. 'To prepare an organic solution. In addition, 70% by weight of silver fine particles (average k diameter of 1.5 m / m, specific surface area of 1.10m2 / g) and 3% by weight of bismuth borosilicate glass fine particles were added to prepare a paste. -33- V. Description of the invention (32) Make the glue of organic component coating film, 50 (TC and 1000 ° C weight of glue, the location of glue coating film, glue coating film firing) The measurement of the back reflectance was performed in the same manner as in Example 1. The measurement results are shown in Table 4. The silver fine particles obtained by screen printing were coated on a 42-inch diagonal glass substrate to obtain a dry film thickness of 6 // m coating film. Then, exposure was performed through a photomask (striped image, image pitch of 25 μm, line width of 100 // m). Then, after exposure, it was developed in a 0.5% ethanolamine aqueous solution, A strip-shaped electrode image was obtained. The glass substrate with the electrode image processed was fired at 80 ° C for 15 minutes, and then fired at 580 ° C for 15 minutes to form an electrode. The electrode figure after firing In the image, the defects such as peeling or disconnection are observed, and the results are shown in Table 6. On the glass substrate on which the electrode was manufactured, an additional electrophoretic layer was formed, and the partition wall image was formed by the method of Example 11 on the electrophoretic layer. Next And apply a fluorescent substance between the partition walls adjacent to the above display member. The fluorescent substance is applied by forming a mouth 1 3 0 // m, the display induction method is used to discharge the fluorescent substance glue from the front end of the nozzle. The fluorescent substance is coated on the side of the partition wall and fired to 25 vm, and the thickness of the fired layer is 25 / / m, firing at 50 (TC for 10 minutes, to create a back substrate for plasma display (hereinafter referred to as PDP). The separately prepared front substrate was adhered to the back substrate with a contact glass, and the content was 50% xenon. Neon gas seals the internal air pressure to 66 5OOPa. In addition, the drive circuit is installed to make the PDP ° -34- 522435 5. Description of the invention (33) Table 5 Carbamate amine compound monomer polymer solution ethylenicity Unsaturated bond concentration (mol / kg) Kind addition amount (%) Weight average molecular weight EO Content rate Kind lean addition amount (%) Kind addition amount (%) Kind addition amount (%) Example 22 νπ 4 18000 30% I 3 m 3 IΠ 15 0.36 Example 23 VII 5 19000 10% Π 2 — 3 IV 15 0.41 Example 24 νπ 7 18000 30% 0 π 3 Melon 15 0.18 Comparative Example 5 — 〇 一一 Π 9 — 1 IV 15 1.05 Table 6 The maximum stress of the organic component coating film weight Minimum exposure dose defect haze (%) (500 ° C / 1000 ° C) (MPa) (MPa) (units) Example 22 0.2 1.02 6 400 0 Example 23 0.3 1.02 7 450 0 Example 24 0.3 1.02 4 1100 0 Comparative Example 5 0.3 1.11 23 300 > 10 Polymer solution I: ethyl cellulose (20% by weight terpineol solution) Polymer solution II: polymethyl acrylate (50% by weight toluene solution) polymer Solution III: styrene / methyl methacrylate / methacrylic acid copolymer (weight composition ratio 30/30/40) for 100 parts by weight of copolymer -35- 522435 V. Description of the invention (34) 40 parts by weight of a polymer polymer solution of propylene acrylate IV: 40% by weight of 100 parts by weight of the copolymer of methyl methacrylate / methacrylic acid copolymer (weight composition ratio 60/40) Parts of propylene acrylate polymer (resin acid value 1 15mgKOH / g) polymer solution V: methyl methacrylate / methacrylic acid copolymer (weight composition ratio 82/18, resin acid value 90mgKOH / g) unit Body I: Dipentaerythritol hexapropionate monomer II: CH2 = C (CH3) CO- (〇CH (CH3) CH2) 9-OC〇C (CH3) CH2 monomer III: propoxylated trimethylolpropane triacrylate amine-I: N, N-diethylamine ethylmethacrylate amine-II: bis (2-hydroxy-3-methacrylic acid) (Oxypropyl) n-propylamine carbamate-I: in the general formula (I), R], R2 is hydrogen, R3 is redox ethylene-propylene oxide copolymer, and R4 is isophorone The content of diisocyanate residues, ethylene oxide units is 30%, and the overall molecular weight is 18,000 urethane-II: in the general formula (I), R1 and R2 are hydrogen, and R3 is redox ethyl. The alkane-propylene oxide copolymer and R4 are isophorone diisocyanate, the content of the ethylene oxide unit is 10%, and the molecular weight of the whole is 19,000. Urethane-III: In the general formula (I), R1 and R2 are hydrogen, R3 is redox ethylene-propylene oxide copolymer, R4 is isophorone diisocyanate, and ethylene oxide unit The content rate was 0%, and the molecular weight of the whole was 42,000. Urethane-IV: In the general formula (I), R1 and R2 are hydrogen, R3 is redox ethylene-propylene oxide copolymer, and R4 is isophorone diisocyanate residue-36- 522435 5. Description of the invention (35), the content of the ethylene oxide unit is 7%, and the overall molecular weight is 27,000 urethane-V: in the general formula (I), R1 and R2 are hydrogen The R3 system is a redox ethylene-propylene oxide copolymer, the R4 system is an isophorone diisocyanate residue, and the content of the ethylene oxide unit is 80%, and the molecular weight of the whole is 24,000,000. Carbamate-VI: In the general formula (I), R !, R2 is hydrogen, R3 is redox ethylene-propylene oxide copolymer, R4 is 丨, 4_cyclohexyl diiso The content of cyanic acid residues and ethylene oxide units is 50%, and the molecular weight of the whole is 1,200 °. Carbamate-VII · In the general formula (I), R1 and R2 are methacrylic acid Group, R3 is redox ethylene-propylene oxide copolymer, R4 is isophorone diisocyanate residue, the content of ethylene oxide unit is 30%, and the molecular weight of the whole is 18,000. . Carbamate-VIII: In the general formula (I), R1 and R2 are acrylic groups, R3 is redox ethylene-propylene oxide copolymer, and R4 is 1,4-cyclohexylene diisocyanate The content of the residue and the ethylene oxide unit was 10%, and the molecular weight of the whole was 19,000. Low melting point glass powder: composition in terms of oxides, L 120: 9%, S 102 • 22%, Al203: 23%, BA: 33%, BaO: 4%, Zn〇: 2%, Mg 〇: 7% (glass transition point 4721, load softening point 51 5 ° C, refractive index 1.59, average particle size 2.5 5 // m) 塡 charge: composition in terms of oxides' Si 02: 38%, B2〇3: 10%, -37-522435 V. Description of the invention (36), Mg0: 5%, Ca02: 4% (

Ba〇: 5%, A 1 203: 3 6%, ZnO: 2%, glass transition point 6 5 2 ° C, load softening point 7 4 6 C, refraction + 丨 5 9 average particle size 2 · 4 μm) Oxide fine particles: The oxide fine particles (average particle diameter of 0.05 # m) are used in the industry. With the paddle of the present invention, it is possible to provide a display member that does not have defects in the image after firing. -38-

Claims (1)

522435 1 year Amendment ^ 90 1 1 No. 2079 "Making Method for Glue, Display Component and Display Component" ίProblem (Amended on December 16, 91) Patent application scope: 1. A glue, which contains In the rubber award, the content of the urethane compound and the inorganic fine particles is 0.1 to 20% by weight, and the content of the inorganic fine particles is 40 to 80% by weight. 2. The glue according to item 1 of the patent application range, wherein the urethane compound contains a urethane compound having an ethylenically unsaturated group. 3. The glue according to item 1 of the patent application range, wherein the molecular weight of the urethane compound is 15,000 to 50,000. 4. The glue according to item 1 of the patent application range, wherein the urethane compound contains ethylene oxide units. 5. The glue according to item 1 of the scope of patent application, wherein the urethane compound is represented by the following general formula (1), R1-(R4-R3) n-R4-r2 (1) Wherein R1 and R2 are each selected from the group consisting of a substituent containing an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and a hydroxyaromatic group; each may be the same or different; Represents an alkylene oxide or epoxy-based oligomer; R4 represents an organic group containing a urethane bond, and η represents a natural number of 1 to 10; 6 · If the glue of the first patent application range, where R3 is an oligomer containing ethylene oxide units and propylene oxide units, and the star of the oligomer is 8 to 70% by weight. 522435 6. Scope of patent application 7. The glue of item 1 of the scope of patent application, which additionally contains an amine compound with ethylenically unsaturated group. 8. The glue according to item 7 of the scope of patent application, wherein the amine compound is a compound represented by the following general formula (3) or (4), R5R6R7N * (3) R5R6N-M-NR7R8 (4) where R5 represents Substituents containing ethylenic unsaturated groups; R6, R7, R8 represent a substituent selected from ethylenic unsaturated groups, hydrogen, alkyl groups having 1 to 20 carbon atoms, aryl groups, aralkyl groups, and hydroxyalkanes R6, R7, and R8 may be the same or different; M is a divalent bonding group. 9 · The glue according to item 丨 of the patent application scope, which further contains a polymer having a carboxyl group. 10. The glue according to item 9 of the application, wherein the polymer having a carboxyl group has an ethylenically unsaturated group. 1 1 · As for the glue in the first scope of the patent application, the inorganic fine particles contain a low melting point glass powder with a softening point of 450 ~ 60 (TC). 1 2 · As in the glue in the first scope of the patent application, the inorganic fine particles contain 60 to 97% by weight of low melting point glass powder and 3 to 40% by weight of the filler with an average particle size of 1 to 4 μm. 1 3 · As in the glue of item 12 of the patent application scope, the inorganic fine particles further contain 30% by weight or less Oxide fine particles with an average particle diameter of 0.00 3 ~ 0.02 μπι. 1 4. For example, the glue of item 1 in the scope of patent application, in which the temperature rises to 500 ° C 522435 6. The scope of patent application and the weight at 1 00 ° c are as follows: It means that (weight of 500 ° C) / (100 (weight of TC)) $ 1.05. 1 5. If the glue in the scope of patent application No. 1 is used, the glue is photosensitive. 1 6 · As in the scope of patent application No. 1 The glue of 5 items, wherein the concentration of ethylenically unsaturated bonds in the glue is 0.2 to 1.0 moles for the glue before 1 kg of active light irradiation. 1 7. As described in item 1 of the scope of patent application Glue, which is used for display. 1 8 · As the glue in the scope of patent application No. 17 The display is a plasma display. 19. A glue is characterized in that a thin film is coated on the silicon wafer as in the patent application No. 1 to form a thin film, and the film shrinks from the difference between the silicon wafer and the silicon wafer. The maximum value of the average film stress calculated from the measurement is 0.1 to 20 MPa. 20. A kind of glue, which contains inorganic fine particles and organic components, and is characterized by a temperature rise to 500 ° C and 100 (the weight at TC is expressed by the following formula, (5 00 ° C weight) / (1000 ° C weight 1.05. 21. A kind of glue, which contains inorganic particles and organic components, is characterized in that the glue is coated on a silicon wafer to form a thin film, And when the temperature is raised to 500 ° C, the maximum value of the average film stress calculated from the difference between the film shrinkage from the silicon wafer is 0.1 to 20 MPa. 22. A method for manufacturing a display member, characterized in that it comprises a urethane-containing compound 1 and 20% by weight of the urethane compound in the dope, and the content of the inorganic fine particles is 40 to 80% by weight. 522435 6. Scope of patent application 23. The method for manufacturing a display member in the range of item 22, wherein the moon's formate compound has an ethylenically unsaturated group. 24. The method for manufacturing a display member in the scope of the patent application, item 22, wherein the molecular weight of the urethane compound is 1. 5000 ~ 50,000. 25. The method for manufacturing a display member according to item 22 of the patent application, wherein the urethane compound contains an ethylene oxide unit. 26. The method for manufacturing the display member according to item 22 of the patent application, in which aminomethyl The acid ester compound is represented by the following general formula (1), R1-(R4-R3) n-R4-R2 (1) wherein R1 and R2 represent a substituent selected from an ethylenically unsaturated group-containing substituent, hydrogen, and carbon number. The alkyl, aryl, aralkyl, and hydroxyaralkyl groups of 1 to 20 may be the same or different; R3 represents an alkylene oxide or an alkylene oxide oligomer; R4 represents a carbamic acid Organic group of ester bond; η represents a natural number of 1-10. 27. The method for manufacturing a display member according to item 26 of the patent application, wherein R3 is an oligomer containing ethylene oxide units and propylene oxide units, and the content of ethylene oxide units in the oligomer is 8 ~ 70% by weight. 28. The method for manufacturing a display member according to item 22 of the application, wherein the glue further contains an amine compound having an ethylenically unsaturated group. 29. The method for manufacturing a display member according to item 28 of the application, wherein the amine compound is a compound represented by the following general formula (3) or (4), r5r6r7n / 、、 Applicable patent range R5R6N-μ-NR7R8 (4) where 'R5 is a substituent containing ethylenic unsaturated group; R6, R7' R8 is a substituent selected from ethylenic unsaturated group, hydrogen For an alkyl group, aryl group, aralkyl group, and hydroxyalkyl group having 1 to 20 carbon atoms, R6, R7, and R8 may be the same or different; M is a divalent bonding group. 3 Q · If the method of manufacturing a display member according to item 22 of the patent application method, which contains a polymer having a carboxyl group. 31. The method for manufacturing a display member according to item 30 of the application, wherein the polymer having a residue has an ethylenically unsaturated group. 3 2 · The method for manufacturing a display member according to item 22 of the application, wherein the inorganic fine particles contain a low-melting glass powder having a softening point of 450 to 600 ° C. 3 3. The method for manufacturing a display member according to item 22 of the scope of patent application, wherein the inorganic fine particles contain 60 to 97% by weight of a low melting point glass powder and 3 to 40% by weight of an average particle size of 1 to 4 μΐΏ. 34. The method for manufacturing a display member according to item 33 of the scope of the patent application, wherein the inorganic fine particles further contain 30% by weight of oxide fine particles having an average particle diameter of 0.003 to 0.02 µm. 3 5 · According to the method of manufacturing the display member No. 22 in the scope of the patent application, wherein the weight of the glue when the temperature rises to 500 ° C and 1 000 ° C is the glue shown in the following formula, (weight of 500 ° C) / ( Weight of 1000 ° C) $ 1.05 ° 3 6. If the method of manufacturing a display component according to item 22 of the patent application 'of which 522435 6. Application of the patent application covers the glue on a silicon wafer to form a thin film, and When the temperature was raised to 500 ° C, the maximum value of the average film stress was calculated from the difference between the film shrinkage from the silicon wafer and 0.1 to 20 MPa. 37. The method for manufacturing a display member according to item 22 of the patent application, wherein the glue is photosensitive. 38. The method for manufacturing a display member according to item 37 of the application, wherein the glue is applied, and then processed by lithography image and then fired. 39. For the method for manufacturing a display component according to item 37 of the application, wherein the concentration of ethylenically unsaturated bonds in the glue is 0.2 to 1.0 mole per 1 kg of the glue before irradiation with active light. 40. The method for manufacturing a display component according to item 22 of the patent application, wherein the display is a plasma display. 41. A plasma display member, which is produced by a manufacturing method including a step of coating a paste containing a urethane compound and inorganic fine particles on a substrate and firing the paste. The content of the acid ester compound is 0.1 to 20% by weight, and the content of the inorganic fine particles is 40 to 80% by weight. 42. A plasma display using a plasma display member produced by a manufacturing method including a step of coating a paste containing a urethane compound and inorganic fine particles on a substrate and firing, The content of the urethane compound is 0.1 to 20% by weight, and the content of the inorganic fine particles is 40 to 80% by weight. 43. A method for manufacturing a display element, which is characterized in that it comprises the steps of applying a glue such as item 20 or 21 on the substrate and firing it 522435 6. Applying for a patent. 44. For the method for manufacturing a display component according to item 43 of the patent application, wherein the display is a plasma display. 45. A plasma display component, which consists of a paste containing inorganic fine particles and organic components. The weight of the paste when heated to 500 ° C and 1,000 ° C is expressed by the following formula, (500 ° C weight ) / (1000 ° C weight) $ 1.05, the glue is coated on a silicon wafer to form a thin film, and when the temperature is raised to 500 ° C, the maximum film stress is calculated from the difference between the film shrinkage and the silicon wafer. Is 0.1 ~ 20Mp a. It is made by the method of coating this glue on the substrate and firing. 46. A plasma display using a plasma display component, the plasma display component is a paste containing inorganic particles and organic components, the paste is heated to 500 ° C and 1 000 ° C The weight is expressed by the following formula: (500 ° C weight) / (1000 ° C weight 1.05), the glue is coated on a silicon wafer to form a thin film, and the film shrinks from the silicon wafer when the temperature rises to 500 ° C. The maximum value of the average film stress calculated by the difference is 0.1 to 20 MPa, which is produced by coating the substrate on the substrate and firing.